EP0470262A1 - Composition d'alliage cuivreux - Google Patents

Composition d'alliage cuivreux Download PDF

Info

Publication number
EP0470262A1
EP0470262A1 EP91904341A EP91904341A EP0470262A1 EP 0470262 A1 EP0470262 A1 EP 0470262A1 EP 91904341 A EP91904341 A EP 91904341A EP 91904341 A EP91904341 A EP 91904341A EP 0470262 A1 EP0470262 A1 EP 0470262A1
Authority
EP
European Patent Office
Prior art keywords
copper alloy
resin
alloy composition
copper
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91904341A
Other languages
German (de)
English (en)
Other versions
EP0470262A4 (en
EP0470262B1 (fr
Inventor
Akinori Yokoyama
Tsutomu Katsumata
Hitoshi Nakajima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Asahi Kasei Kogyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Chemical Industry Co Ltd, Asahi Kasei Kogyo KK filed Critical Asahi Chemical Industry Co Ltd
Publication of EP0470262A1 publication Critical patent/EP0470262A1/fr
Publication of EP0470262A4 publication Critical patent/EP0470262A4/en
Application granted granted Critical
Publication of EP0470262B1 publication Critical patent/EP0470262B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0425—Copper-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0466—Alloys based on noble metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C22C5/08—Alloys based on silver with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/4038—Through-connections; Vertical interconnect access [VIA] connections
    • H05K3/4053—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques
    • H05K3/4069—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques for via connections in organic insulating substrates

Definitions

  • the present invention relates to copper alloy composition pastes having high electroconductivity, oxidation resistance and electromigration resistance, and to electric conductors obtained by the use of the pastes.
  • the pastes are useful for electromagnetic shielding, and as electrically conductive adhesives, pastes for conductive circuits, pastes for electrodes, pastes for screen printing, pastes for printing resistance terminals, pastes for through holes, materials for contact, etc.
  • dispersions have been obtained by adding an organic binder and optionally a solvent and additives to powder of, for example, any of the following metals: noble metals, such as gold, platinum, palladium, silver, and silver-palladium [for instance, Jap. Pat. Appln. Kokai (Laid-Open) Nos. SHO 56 (1981)-70064, SHO 51 (1976)-124655, SHO 59 (1984)-45355, and HEI 1 (1989)-98674], nickel [for instance, Jap. Pat. Appln. Kokai (Laid-Open) SHO 58 (1983)-53966], silver-plated copper [for instance, Jap. Pat. Appln.
  • the conventional electrically conductive pastes have the following defects. Copper is not expensive but oxidation tends to decrease its electroconductivity. Addition of an antioxidant to paste obtained with copper powder has also been tried. In such case, in an early stage, copper oxide is removed from particle surfaces and electroconductivity can be attained. But, after the paste is made into a coating film, the contact resistance is gradually increased at high temperatures or high humidities, resulting in low electroconductivity. Electrically conductive pastes obtained by the use of silver powder are well known but involve an electromigration problem.
  • the present invention relates to inexpensive electrically conductive pastes which have an excellent electroconductivity, a high oxidation resistance for a long period of time, and a high electromigration resistance.
  • One aspect of the present invention is directed to a method for stabilizing an electrically conductive paste for a long period of time, particularly by improving the oxidation resistance and the migration resistance.
  • Copper alloy powder used in the present invention is produced by atomization. Gas atomization and water atomization are preferable. In particular, inert gas atomization is preferable.
  • inert gas atomization used in the present invention the process disclosed by the present inventors in U.S. Patent Application Serial No. 07/395531 is preferably employed. This process is as follows. For example, a copper-silver mixture or alloy having a specified composition is melted in a crucible by high-frequency induction heating in an inert atmosphere or in vacuo.
  • the term "inert atmosphere” means an atmosphere which does not react with the melt at all or reacts therewith very slowly. For instance, an atmosphere composed mainly of nitrogen, helium, hydrogen or argon is preferable.
  • the melt is jetted into an inert gas atmosphere from a nozzle attached to the end of the crucible. Simultaneously with the jetting, the inert gas which has been compressed is thermally adiabatically expanded and the thus-generated high-speed gas stream is jetted against the melt to atomize the melt.
  • the inert gas used here is a gas which does not react with the melt of such a composition at all or reacts therewith very slowly.
  • nitrogen, helium, argon, hydrogen and mixtures thereof are preferable.
  • the oxygen content of the gas is preferably 2% or less, more preferably 0.1% or less.
  • the pressure of the gas (immediately before the expansion) is preferably 5 kg/cm 2 G or more, more preferably 15 kg/cm 2 G.
  • the speed of the high-speed gas stream is preferably 50 m/sec or more, more preferably 100 m/sec or more, most preferably 300 m/sec or more, at the outlet of a gas nozzle.
  • the mass velocity ratio of the gas to the melt (the mass velocity of the gas/the mass velocity of the melt) is preferably 0.1 or more, more preferably 1 or more.
  • the cooling temperature in this case is preferably not higher than 109 0 C/sec and not lower than 1020 C/sec, more preferably not higher than 10 9 ° C/sec and not lower than 107 C/sec.
  • a melt of the aforesaid composition is jetted from the end of a nozzle attached to the crucible.
  • pressurized water is jetted from a nozzle against the melt jetted from the end of the crucible, and collides with the melt of the aforesaid composition to make the melt into fine particles.
  • the fine particles are rapidly cooled and solidified.
  • the ratio of the mass velocity of water to that of the melt is preferably 10 or more, more preferably 40 or more.
  • the speed of water at the outlet of the water nozzle is preferably 80 m/sec or more, more preferably 100 m/sec or more.
  • the pressure at jetting of pressurized water from the end of the nozzle is preferably 50 kg/cM 2 G or more, more preferably 100 kg/c M 2 G or more.
  • the silver concentration in the surface of each of such copper alloy particles used in the present invention is higher than the average silver concentration of the whole particle, and the particle has a region near the surface in which the silver concentration increases with a decrease of the distance to the surface.
  • the silver concentration in the surface is 2.1 times or more as high as the average silver concentration.
  • the value x for silver is preferably 0.005 ⁇ x ⁇ 0.3, more preferably 0 01 ⁇ x ⁇ 0.25.
  • the silver concentration in the surface is higher than the average silver concentration.
  • USSN U.S. Patent. Application Serial No. 07/395531
  • a mechanism by which silver having a low melting point is condensed in the surface can be conjectured as follows. For example, fine metal droplets formed by the collision of the melt with the high-speed gas stream are rapidly cooled and solidified while flowing at a high speed in company with the high-speed gas stream. It can be speculated that, in this solidification process, a liquid phase rich in silver with a low melting point is driven out to the surface and solidified later, resulting in production of particles in which silver has been condensed in the surface.
  • Alloy powder in which the value x for silver exceeds 0.4 can be used particularly when oxidation resistance at high temperatures is required.
  • the alloy powder in which the value x for silver exceeds 0.4 has the following advantage.
  • the silver concentration in the surface is high, and silver spreads fairly deep in the inside of each particle, thus preventing an minimizing oxidation of copper.
  • the powder has a high electromigration resistance.
  • Powder produced by rapid cooling and solidification by water atomization contains a large amount of particles of irregular shape. Such a powder produced by water atomization can be classified as spherical particles in the present invention.
  • the value x for silver used in the present specification means Ag/(Ag + Cu) (atomic ratio).
  • the silver concentrations in and near the surface were measured by means of an XPS (KRATOS XSAM 800, an X-ray photoelectron spectrochemical analyzer mfd. by KRATOS CO., LTD.).
  • the term “the value y for copper” means Cu/(Ag + Cu) (atomic ratio).
  • a carbon pressure-sensitive adhesive double-coated tape having electroconductivity was attached to a specimen carrier, and sample powder was gently adhered to the double-coated tape to cover the tape completely, with caution so as not to deform the sample powder.
  • the conditions of measurement of the silver concentrations were as follows. K a-ray of magnesium (voltage 12 KV, current 10 mA) were radiated upon the sample, and the angle of taking out photoelectrons was adjusted to 90° with the surface of the sample. The measurement was carried out at a pressure of 10- 8 torr in a chamber.
  • Etching was carried out under the following conditions; acceleration voltage of an argon ion gun: 3 keV, the angle of incidence of argon ion beam upon the surface of the sample: 45°, pressure in a chamber: 10- 7 torr, etching time: 10 min.
  • the silver concentrations were determined by repeating the measurement and the etching alternately five times each, and the average of the first two measurements was taken as the silver concentration in the surface.
  • the average silver concentration was measured by means of an ICP (an inductively coupled plasma emission spectrochemical analyzer) by using a solution prepared by dissolving the sample in concentrated nitric acid.
  • ICP an inductively coupled plasma emission spectrochemical analyzer
  • the copper alloy powder used in the present invention has an average particle size of from 0.1 to 100 ⁇ m. When the average particle size is less than 0.1 ⁇ m, the contact resistance is increased, so that the electroconductivity is decreased. When it exceeds 100 ⁇ m, the screen printability is decreased.
  • the average particle size is preferably from 0.1 to 50 am, more preferably from 0.5 to 30 am.
  • SALD 1100 laser diffraction type particle size distribution meter
  • the shape of particles is preferably a spherical shape, scaly shape or a mixture thereof.
  • the particles can be mechanically flattened by conventional means. Such means include, for example, stamp mill and ball mill.
  • the copper alloy powder used in the present invention optionally includes metals and semi-metals, for example, Al, Zn, Sn, Pb, Si, Mn, Bi, Mo, Cr, lr, Nb, Sb, B, P, Mg, Li, C, Na, Ba, Ti, In, Au, Pd, Pt, Rh, Ru, Zr, Hf, Y and La, and compounds thereof at the time of melting so long as they do not deteriorate characteristics of the powder.
  • metals and semi-metals for example, Al, Zn, Sn, Pb, Si, Mn, Bi, Mo, Cr, lr, Nb, Sb, B, P, Mg, Li, C, Na, Ba, Ti, In, Au, Pd, Pt, Rh, Ru, Zr, Hf, Y and La, and compounds thereof at the time of melting so long as they do not deteriorate characteristics of the powder.
  • the powder of the present invention is optionally used in admixture with powder comprising or consisting of any of numerous metals and semi-metals, for example, Al, Zn, Sn, Pb, Si, Mn, Bi, Mo, Cr, lr, Nb, Sb, B, P, Mg, Li, C, Na, Ba, Ti, In, Au, Ag, Cu, Pd, Pt, Rh, Ru, Zr, Hf, Y and La, and compounds thereof.
  • any of numerous metals and semi-metals for example, Al, Zn, Sn, Pb, Si, Mn, Bi, Mo, Cr, lr, Nb, Sb, B, P, Mg, Li, C, Na, Ba, Ti, In, Au, Ag, Cu, Pd, Pt, Rh, Ru, Zr, Hf, Y and La, and compounds thereof.
  • thermosetting resins selected from the group consisting of thermosetting resins, thermoplastic resins, photo-setting resins, electron-beam-setting resins, photo-degradable resins and electron-beam- degradable resins are used.
  • suitable thermoplastic resins are thermoplastic acrylic resins, alkyd resins, vinyl chloride resins, urethane resins, polyester resins, vinyl chloridevinyl acetate copolymers, vinyl acetate resins, ethylenevinyl acetate copolymers, polycarbonate resins, styrene resins, etc.
  • thermosetting resins there are preferably used one or more members selected from the group consisting of epoxy resins, phenolic resins, amino resins, alkyd resins, polyurethane resins, polyester resins, thermosetting acrylic resins, polyimide resins, melamine alkyd resins, and modified resins obtained from them.
  • the epoxy resins include, for example, bisphenol A type epoxy resins with a molecular weight of from 380 to 8,000, epoxy phenolic novolak type resins, epoxy cresol novolak type resins, brominated bisphenol A type epoxy resins, alicyclic epoxy resins, chain epoxy resins, polyalkylene ether type epoxy resins, polyglycidyl ether type epoxy resins, diglycidyl ether type epoxy resins, diglycidyl ester type epoxy resins, dimer acid diglycidyl ester type epoxy resins, epoxyacrylate resins, and modified epoxy resins obtained from them, such as epoxy resins modified at the terminal phenolic hydroxyl group, fatty-acid-modified epoxy resins, and urethane-modified epoxy resins.
  • the diluents include, for example, diglycidyl ether, ethylene glycol diglycidyl ether, 1,3-butanediol diglycidyl ether, butadiene dioxide, diethylene glycol diglycidyl ether, vinylcyclohexane diepoxide, triglycidyl cyanurate, N-diglycidylamine, divinylbenzene diepoxide.
  • the diluents are not limited thereto.
  • the phenolic resins include novolak type phenolic resins, resol type phenolic resins, alkylphenol resol type resins, xylene-resin-modified resol type resins, resin-modified phenolic resins, etc. Of these, the resol type resins and the modified resol type resins are preferable.
  • the amino resins include, for example, methylated melamine resins, butylated melamine resins, benzoguanamine resins, urea resins, and butylated urea resins. It is preferable to use the amino resins as cross-linking agents for the thermosetting acrylic resins, the phenolic resins and the epoxy resins.
  • the polyimide resins include, for example, condensate type polyimides, bismaleimide resins, and adduct type polyimides having an acetylene group or the like at the end of the molecule.
  • curing accelerator there can, if necessary, be used well-known curing agents, such as organic polyamines, acid anhydrides, dicyandiamide, benzoguanamine, biguanide, alkylphenyl- biguanides, diphenylbiguanide, boron trifluoride, amine compounds, etc.
  • curing agents such as organic polyamines, acid anhydrides, dicyandiamide, benzoguanamine, biguanide, alkylphenyl- biguanides, diphenylbiguanide, boron trifluoride, amine compounds, etc.
  • the preferred acrylic resins are those whose functional groups are as follows: the acid value (-COOH) is from 10 to 80 mg/g, particularly preferably from 20 to 75 mg/g, and the hydroxyl value (-OH) is from 40 to 250 mg/g, particularly preferably from 50 to 200 mg/g.
  • the acid value (-COOH) is from 10 to 80 mg/g, particularly preferably from 20 to 75 mg/g
  • the hydroxyl value (-OH) is from 40 to 250 mg/g, particularly preferably from 50 to 200 mg/g.
  • an acrylic resin having a hydroxybutyl group acrylic resin having a hydroxybutyl group.
  • acrylic resins having a molecular weight of 2,400 or more can be used, though the molecular weight is preferably not more than 16,000 and not less than 4,500.
  • the average molecular weight of the polyester resins or the alkyd resins is preferably 4,000 or more, more preferably 7,000 or more.
  • polyurethane resins urethane prepolymers capable of yielding urethane can be used.
  • Polyurethane resins composed mainly of a blocked isocyanate prepolymer obtained by blocking the terminal active isocyanate group with an active-hydrogen compound are preferably used.
  • a heating means includes a box-type hot-air convection furnace, continuous heating furnace, muffle furnace, near-infrared rays furnace, far-infrared rays furnace, vapor phase heating device, etc. Conventional means may be used. Any drying temperature or heat curing temperature may be employed so long as it does not have an undesirable influence on characteristics of a substrate. The drying temperature or the heat curing temperature is suitably and conventionally chosen. Curing may be conducted in air (oxygen content: 20%) or in an atmosphere having a lower oxygen content or containing no oxygen.
  • the photo-setting resins include ultraviolet-setting resins and visible-ray-setting resins.
  • the ultraviolet-setting resins are preferable.
  • the photopolymerizable oligomer its molecule is a low-molecular-weight reactive molecule (molecular weight: hundreds to thousands).
  • the oligomer has, as functional groups, two or more acrylic or methacrylic groups introduced into its skeleton, such as a polyester skeleton, epoxy skeleton or urethane skeleton.
  • the oligomer includes, for example, epoxyacrylate, urethane acrylate, polyester acrylates and polyether acrylates.
  • the monofunctional acrylates and methacrylates include, for example, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, isobornyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, N,N-dimethylaminoethyl acrylate, glycidyl methacrylate, lauryl acrylate, polyethylene acrylate 90 methacrylate, and trifluoroethyl methacrylate.
  • the polyfunctional acrylates include, for example, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol acrylate, polyethylene glycol (400) diacrylate, tripropylene glycol diacrylate, bisphenol A diethox- ydiacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate.
  • Monofunctional monomers such as styrene, vinyltoluene, vinyl acetate, N-methylpyrrolidone, etc, can be used as the reactive monomers having a vinyl group.
  • Photoinitiator used together with the oligomer or the monomer.
  • Photoinitiators of the acetophenone type, thioxane type, benzoin type and peroxide type are optionally used.
  • the photoinitiator includes, for example, diethoxyacetophenone, 4-phenoxydichloroacetophenone, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, 4-phenylbenzophenone, acrylated benzophenone, thioxanthone, and 2-ethylanthraquinone.
  • the photoinitiator assistant useful in the present invention is one which is not itself activated by ultraviolet irradiation, but which makes the curing reaction efficient because its simultaneous use with the photoinitiator accelerates initiation reaction more markedly than employment of the photoinitiator alone.
  • Photoinitiator assistants such as aliphatic and aromatic amines, for example, triethanolamine, N-methyldiethanolamine, Michler's ketone and 4,4-diethylaminophenone, are useful for this purpose.
  • an ultraviolet-emitting apparatus comprising a mercury lamp
  • a well-known apparatus may be used.
  • a light source of 100 watt/cm or more is preferable.
  • a sufficient irradiation time is from several seconds to several tens of seconds.
  • Preferable resins include polyester acrylate resins, epoxyacrylate resins, and polyurethane acrylate resins.
  • Exemplary electron-beam-setting resins include the above-exemplified photo-setting resins (photopolymerizable oligomers and photopolymerizable monomers).
  • photo-setting resins photopolymerizable oligomers and photopolymerizable monomers.
  • electrons accelerated at a high voltage have a high curing capability because of their high energy and higher penetrability than that of light; moreover, they permit curing at room temperature.
  • the aforesaid oligomer or monomer absorbs the electron beam to generate ions or a radical, the photoinitiator and the photoinitiator assistant are not necessary in principle.
  • Electron beam curing may be carried out by a conventional method. For example, when the coating film thickness is 100 I.Lm or less, an accelerating voltage of 150 kV or more is preferable and a conventional method can be employed.
  • the copper alloy composition of the present invention contains organic binder(s) in an amount of from 5 to 200 parts by weight per 100 parts by weight of the copper alloy powder.
  • organic binder(s) When the amount of the organic binder(s) is less than 5 parts by weight, the amount of resin contained in the composition is insufficient to bind the electrically conductive metal powder in a coating film, so that the electroconductivity and the mechanical strength are decreased.
  • the amount of the organic binder(s) exceeds 200 parts by weight, the amount (concentration) of the electrically conductive metal powder is inadequate to attain desired electroconductivity.
  • the amount of the organic binder(s) is preferably from 5 to 100 parts by weight, more preferably from 5 to 50 parts by weight.
  • a solvent is optionally included therein.
  • Such solvent is preferably contained in the composition in an amount of from 0 to 100 parts by weight, inclusive, per 100 parts by weight of the sum of the copper alloy powder and the organic binder(s).
  • Well-known solvents are useful, and they naturally depend on the particular resin.
  • Preferred solvents include aromatic compounds, such as toluene, xylene, etc; ketones, such as methyl ethyl ketone, methyl isobutyl ketone, etc.; esters, such as butyl acetate, ethyl acetate, etc.; ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monoallyl ether, ethylene glycol dodecyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monoisopropyl ether and its acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glyco
  • the copper alloy composition of the present invention contains at least one additive capable of removing copper oxide, in an amount of 0.01 to 50 parts by weight per 100 parts by weight of the copper alloy powder.
  • the additive can reduce copper oxide on the surfaces of particles constituting the powder, or can dissolve the copper oxide to remove the same from the surfaces.
  • the mechanism of electric conduction of the copper alloy composition of the present invention is such that the composition has electroconductivity by virtue of contacts between particles. Therefore, characteristics of the surfaces of the particles are important.
  • silver is contained in the surfaces of the particles, and silver contacts between the particles are sufficiently secured by removing or reducing the copper oxide present in such surfaces. Accordingly, the composition is stable for a long period of time with respect to oxidation resistance of the surfaces of the particles at high temperatures or high humidities.
  • the amount of the additive used when it is less than 0.1 part by weight, insufficient electroconductivity can be attained. When it exceeds 50 parts by weight, the additive is adsorbed on the surfaces of the particles to decrease the electroconductivity. Therefore, it is preferable to add the additive in an amount required on the basis of the amount of copper oxide present in the surfaces of the particles.
  • the amount is preferably from 1 to 50 parts by weight, more preferably from 1 to 30 parts by weight.
  • Suitable additives according to the present invention include one or more members selected from the group consisting of fatty acids, dicarboxylic acids, oxycarboxylic acids and metal salts thereof, phenol compounds, metal-chelate-forming agents, higher fatty amines, organotitanium compounds, rosin, and anthracene and derivatives thereof.
  • the fatty acids include saturated fatty acids (e.g. acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, pen- tadecylic acid, heptadecylic acid, stearic acid, non- adecanoic acid, arachic acid and behenic acid), unsaturated fatty acids (e.g.
  • saturated fatty acids e.g. acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, pen- tadecylic acid, heptadecylic acid, stearic acid, non- adecanoic acid, arachic acid and behenic acid
  • unsaturated fatty acids e.g.
  • metal salts thereof e.g. copper salts, iron salts, magnesium salts, manganese salts and silver salts.
  • metal salts of higher fatty acids, or fatty acids having 13 or less carbon atoms and metal salts thereof are preferably used.
  • the dicarboxylic acids include saturated aliphatic dicarboxylic acids (e.g. oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid), unsaturated aliphatic dicarboxylic acids (e.g. maleic acid and fumaric acid), aromatic dicarboxylic acids (e.g. phthalic acid, isophthalic acid and terephthalic acid), metal salts thereof (e.g. copper salts, iron salts, magnesium salts, manganese salts and silver salts), and anhydrides thereof.
  • saturated aliphatic dicarboxylic acids e.g. oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid
  • unsaturated aliphatic dicarboxylic acids e.g. male
  • the oxycarboxylic acids include aliphatic oxycarboxylic acids (e.g. glycolic acid, lactic acid, hydroacrylic acid, a-oxybutyric acid, glyceric acid, tartronic acid, tartaric acid and citric acid), aromatic oxycarboxylic acids (e.g. salicyclic acid, p- and m-oxybenzoic acid, mandelic acid, tropic acid, ox- yphenylacetic acid, resorcylic acid, orsellinic acid, gentisic acid, protocatechuic acid, caffeic acid and umbellic acid), metal salts thereof.
  • the metal includes copper, manganese, silver, iron, magnesium, cobalt, etc.
  • the phenol compounds include monohydric, dihydric and trihydric phenols and derivatives thereof, for example, phenol, cresol, 3,5-xylenol, carvacrol, thymol, naphthol, catecol, resorcin, hydroquinone, methylhydroquinone, tert-butylhydroquinone, chlorohydroquinone, phenylhydroquinone, 1,2,4-benzenetriol, pyrogallol, and fluoroglucitol.
  • the metal chelate forming agents include, for example, amino alcohols (e.g. ethanolamine, diethanolamine, triethanolamine, and derivatives thereof), amine compounds (e.g. ethylenediamine, triethylenediamine and triethylenetetramine), and acetylacetone and its derivatives (e.g. trifluoroacetylacetone, hexafluoroacetylacetone and benzylacetone).
  • amino alcohols e.g. ethanolamine, diethanolamine, triethanolamine, and derivatives thereof
  • amine compounds e.g. ethylenediamine, triethylenediamine and triethylenetetramine
  • acetylacetone and its derivatives e.g. trifluoroacetylacetone, hexafluoroacetylacetone and benzylacetone.
  • the higher fatty amines are preferably those having 8 to 22 carbon atoms which are soluble in solvents. They include, for example, saturated monoamines, such as stearylamine, palmitylamine, behenylamine, cetylamine, octylamine, decylamine, laurylamine, etc.; and unsaturated monoamines, such as oleylamine, etc.; diamines, such as stearylamine, propylenediamine, oleyl- propylenediamine, etc.
  • organotitanium compounds there can be exemplified R i -Ti-(R 2 ) 3 (wherein R 1 is an alkoxy group having 1 to 4 carbon atom, preferably 1 to 3 carbon atoms, and R 2 is a carboxylic acid ester having 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms).
  • R 1 is an alkoxy group having 1 to 4 carbon atom, preferably 1 to 3 carbon atoms
  • R 2 is a carboxylic acid ester having 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms.
  • Specific examples of the organotitanium compounds are isopropyltriisostearoyl titanate and isopropyltrioctanoyl titanate.
  • the anthracene and derivatives thereof include, for example, anthracenecarboxylic acid.
  • the rosin includes, for example, modified rosins, such as partially hydrogenated rosin, completely hydrogenated rosin, esterified rosin, mal- einated rosin, disproportionated rosin, polymerized rosin, etc.
  • the amount of the additive one or more additives selected from the above-exemplified additives are added in an amount of from 0.1 to 50 parts by weight per 100 parts by weight of the copper alloy powder.
  • the amount is less than 0.1 part by weight, sufficient electroconductivity cannot be attained.
  • the amount exceeds 50 parts by weight, bleeding from a coating film occurs, so that electroconductivity is decreased.
  • the amount is preferably from 1 to 50 parts by weight, more preferably from 1 to 30 parts by weight.
  • the copper alloy composition of the present invention provides an electrically conductive paste having high electroconductivity and electromigration resistance.
  • well-known additives such as viscosity adjustors, diluents, suspending agents, leveling agents, anti-foaming agents, silane coupling agents, titanium coupling agents, aluminum coupling agents, etc., are optionally incorporated therein.
  • the copper alloy composition of the present invention is useful in conventional printing methods and coating methods, for example, screen printing, spray coating, brush coating, bar coating, doctor blade coating, Flexshar printing, micro dispenser coating, gravure printing, offset printing, pen writing method, etc.
  • screen printing is preferable.
  • the screen mesh is preferably from 50 to 400 mesh, more preferably from 150 to 400 mesh.
  • a screen mesh of 200 mesh or more is particularly preferable.
  • the composition can be applied, for example, on hard or flexible substrates composed of a glass-epoxy resin substrate, paper-phenolic resin substrate, paper-epoxy resin substrate, polyimide resin substrate, polyester resin substrate, BT resin substrate, polysulfone resin substrate, polyether-sulfone resin substrate, polyether-imide resin substrate, polybutadiene resin substrate, polyphenylene ether resin substrate, polyphenylene sulfide resin substrate, or glass-polyimide resin substrate; ceramic substrates, such as an alumina substrate, aluminum nitride substrate, etc.; metal substrates, such as an aluminum substrate, a stainless steel substrate, an enamel substrate, etc.
  • the composition is preferably a copper alloy composition with a binder composed mainly of a vinyl resin (e.g. a vinyl chloridevinyl acetate copolymer) or a saturated polyester or polyurethane type resin.
  • a vinyl resin e.g. a vinyl chloridevinyl acetate copolymer
  • a saturated polyester or polyurethane type resin e.g. a vinyl chloridevinyl acetate copolymer
  • the copper alloy composition of the present invention is used as a paste for electromagnetic shielding, it is preferable to print the composition on the surface of a substrate for printed circuit to achieve shielding.
  • the composition is useful for coating plastic boxes of word processors, housings for machinery and tools for computers, card readers, measuring instruments, car telephones, keyboards, medical instruments, musical instruments, CRT, etc.
  • the copper alloy composition of the present invention when used as an electrically conductive additive, it can be used, for example, as an adhesive for taking out a lead wire from the electrode of a quartz crystal oscillator, an adhesive for adhesion between molded carbon and a metal, an electrically conductive adhesive for adhesion between glass portions in a liquid crystal display (LCD), an adhesive for adhering elements of IC, LSI, LED, SAW filter or the like to a lead frame or a substrate (in particular, an adhesive for IC die bonding), an adhesive for the Cds part of a photoconductive element and the lead wire of a potentiometer, an adhesive for circuit repair and materials which cannot be directly soldered, and an adhesive for materials which cannot be heated at a high temperature.
  • an adhesive for taking out a lead wire from the electrode of a quartz crystal oscillator an adhesive for adhesion between molded carbon and a metal, an electrically conductive adhesive for adhesion between glass portions in a liquid crystal display (LCD), an adhesive for adhering elements of
  • the inner walls and intermediate edges of the through holes which have been formed in a printed circuit board by punching or the like are covered with the composition, or the holes are filled with the composition.
  • screen printing or Flexshar printing is preferably employed.
  • the electroconductivity (volume resistivity) of a coating film formed of the copper alloy composition of the present invention was measured by a four- probe technique.
  • a electromigration test was carried out in the following manner. A voltage of 10 V was applied between two coating films formed at a distance of 1 mm from each other, and 0.2 ml of a water drop was added between the films. Then, the leakage current was measured, and the time required for the current to exceed 100 /1.m was called "migration time".
  • the shielding effect in the frequency range of 100 kHz to 1 GHz was measured by using a wave guide, a spectroanalyzer and a tracking generator, and the results obtained were expressed in decibels (dB).
  • the electromagnetic interference shielding characteristics are preferably at least 30 dB.
  • Electroconductive characteristics for through holes were examined in the following manner. Each composition was printed by screen printing (320 mesh) under pressure on a paper-phenol resin substrate having 30 holes of 1.5, 1, 0.5 and 0.3 mm0 formed by reducing the pressure to some extent on the side reverse to the side on which printing is conducted, so as to fill up the holes completely. After heating, the composition was cured by a method suitable for the composition.
  • a cured product of the composition of the present invention can be trimmed by means of a laser or the like.
  • the present invention provides a copper alloy composition having high electroconductivity, oxidation resistance and electromigration resistance.
  • This composition has excellent characteristics as a paste for electromagnetic shielding, an electrically conductive additive, a paste for conductive circuit, an electrically conductive paste for electrode, and a paste for through hole.
  • the silver concentration varied from 0.05, to 0.04, to 0.03, to 0.02 and to 0.01, starting from the surface.
  • the silver concentration in the surface was 0.045.
  • the silver concentration in the surface was 7.5 times as high as the average silver concentration.
  • Example 2 In the same manner as in Example 1, 314.325 g of copper particles and 5.395 g of silver particles were melted by high-frequency induction heating. The copper and silver particles were heated up to 1680°C to be melted, after which nitrogen gas (99.7% or more) with a pressure of 20 k/cm 2 G was jetted against a melt jetted from the end of a nozzle, at a mass velocity ratio of the gas to the melt of 1.5 to atomize the melt. In this case, the linear velocity of the gas at the outlet of a gas nozzle was 120 m/sec. The powder thus obtained was composed of spherical particles having an average particle size of 19 ⁇ m.
  • the silver concentrations near the surface were 0.07, 0.06, 0.05, 0.04 and 0.03, starting from the surface.
  • the silver concentration in the surface was 0.065.
  • the silver concentration in the surface was 6.5 times as high as the average silver concentration.
  • Example 2 In the same manner as in Example 1, 285.75 g of copper particles and 53.95 g of silver particles were melted in a graphite crucible. The copper and silver particles were heated up to 1570°C to be melted, after which the melt was jetted from the end of the crucible, and at the same time, nitrogen gas (99.9% or more) was jetted with a pressure of 20 k/cm 2 G against the melt at a mass velocity ratio of the gas to the melt of 2 to atomize the melt. In this case, the linear velocity of the gas at the outlet of a gas nozzle was 100 m/sec, and the powder thus obtained had an average particle size of 19 am.
  • the silver concentrations near the surface were 0.72, 0.65, 0.55, 0.5 and 0.48, starting from the surface.
  • the silver concentration in the surface was 0.685.
  • the silver concentration in the surface was 6.85 times as high as the average silver concentration.
  • Example 2 In the same manner as in Example 1, 254 g of copper particles and 107.9 g of silver particles were melted by high-frequency induction heating. The copper and silver particles were heated up to 1800 C, after which nitrogen gas (99.9% or more) was jetted with a pressure of 15 k/cm 2 G against the melt jetted from the end of a crucible into an inert atmosphere (nitrogen), at a mass velocity ratio of the gas to the melt of 2 to atomize the melt. In this case, the linear velocity of the gas at the outlet of a gas nozzle was 80 m/sec. The powder thus obtained had an average particle size of 20 ⁇ m.
  • the silver concentrations near the surface were 0.8, 0.75, 0.7, 0.65 and 0.6, starting from the surface.
  • the silver concentration was 0.775.
  • the silver concentration in the surface was 3.85 times as high as the average silver concentration.
  • Example 2 In the same manner as in Example 1, 206.375 g of copper particles and 188.825 g of silver particles were heated up to 1500 C by high-frequency induction heating to be melted. Then, the melt was jetted into an inert atmosphere (nitrogen) from the end of a crucible. Simultaneously with the jetting, nitrogen gas (99.9% or more) was jetted with a gas pressure of 15 k/cm 2 G against the melt at a mass velocity ratio of the gas to the melt of 2 to atomize the melt. In this case, the linear velocity of the gas at the outlet of a gas nozzle was 90 m/sec. The powder thus obtained had an average particle size of 18 ⁇ m.
  • the silver concentrations near the surface were 0.88, 0.8, 0.75, 0.7 and 0.65, starting from the surface.
  • the silver concentration in the surface was 0.84.
  • the silver concentration in the surface was 2.4 times as high as the average silver concentration.
  • Example 2 In the same manner as in Example 1, 9.525 g of copper particles and 523.315 g of silver particles were heated up to 1800°C by high-frequency induction heating to be melted.
  • the melt was jetted from the end of a crucible, and, at the same time, nitrogen gas (99.9% or more) was jetted with a gas pressure of 50 k/cm 2 G against the melt at a mass velocity ratio of the gas to the melt of 2.3 to atomize the melt.
  • the linear velocity of the gas at the outlet of a gas nozzle was 180 m/sec at the collision position.
  • a 10 cm x 10 cm x 50 ⁇ m coating film was formed on a glass-epoxy resin substrate in the same manner as described above. After standing at 60 C and 90% RH for 1,000 hours, the shielding characteristics in the frequency range of 100 kHz to 1 GHz were measured. Consequently, a marked shielding effect of 50 dB was obtained at 300 MHz.
  • a composition prepared in the same manner as described above was introduced into the through holes of 1, 0.5 and 0.3 mm0 of a paper-phenolic resin substrate by screen printing (250 mesh) under a vacuum of 700 mg while pulling the substrate from the side reverse to the side on which the screen printing was conducted. Then, the composition was heat-cured at 230 C for 10 minutes. The cured product filled up the through holes completely and had such a high electroconductivity that its electric resistance was 0.01 9 between the obverse and reverse of the substrate.
  • the same composition as prepared in the above was applied, and a cured film was formed. Consequently, the migration time was 285 seconds. As a result of a humidity resistance test, the percentage change was found to be 2% or less. The result of the cross-cut adhesion test was 100/100.
  • the cured film had a volume resistivity of 1 x 10- 4 O . cm.
  • the result of the migration test was 250 seconds.
  • the percentage change after 1,000 hours was found to be 10% or less.
  • the result of the cross-cut adhesion test was 100/100.
  • AER 337 mfd. by Asahi Chemical Industry Co.
  • a composition obtained in the same manner as described above was introduced into the through holes of 1, 0.5 and 0.3 mm0 of a paper-phenolic resin substrate by screen printing (250 mesh) under a vacuum of 700 mmHg while pulling the substrate from the side reverse to the side on which the screen printing was conducted.
  • the electric resistance of a cured product of the composition between the obverse and the reverse of the substrate was as high as 3 Q.
  • a composition obtained in the same manner as described above was applied on a glass-epoxy resin substrate to form a 10 cm x 10 cm x 50 ⁇ m coating film, which was then heat-cured.
  • the cured film was allowed to stand at 60 C and 90% RH for 1,000 hours, and the shielding characteristics in the frequency range of 100 kHz to 1 GHz were measured. Consequently, the cured film showed a low shielding effect of only 10 dB.
  • the copper alloy composition of the present invention is excellent in properties, such as electroconductivity, oxidation resistance and migration resistance. Therefore, electromagnetic shielding using this composition, and materials comprising this composition (e.g. electrically conductive adhesive, pastes for conductive circuits, pastes for electrodes, pastes for screen printing, pastes for printing resistance terminals, pastes for through holes, and materials for contact) exhibit excellent performance characteristics.
  • electrically conductive adhesive e.g. electrically conductive adhesive, pastes for conductive circuits, pastes for electrodes, pastes for screen printing, pastes for printing resistance terminals, pastes for through holes, and materials for contact

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Conductive Materials (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Powder Metallurgy (AREA)
  • Non-Adjustable Resistors (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

Composition d'alliage cuivreux comprenant 100 parts en poids d'un alliage cuivreux en poudre de la formule générale AgxCuy (dans laquelle 0,001 x 0,999, 0,001 y 0,999 et x + y = 1), 5 à 200 parts en poids d'un liant organique et 0,01 à 100 parts en poids d'un additif qui sert à éliminer les oxydes de cuivre; et pâte pour sérigraphie, écran d'ondes électromagnétiques, adhésif conducteur, pâte pour électrodes et pâte pour trous débouchants, préparés à l'aide de cette composition.
EP91904341A 1990-02-23 1991-02-22 Composition d'alliage cuivreux Expired - Lifetime EP0470262B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2041091A JP2702796B2 (ja) 1990-02-23 1990-02-23 銀合金導電性ペースト
JP41091/90 1990-02-23
JP4109190 1990-02-23
PCT/JP1991/000229 WO1991013445A1 (fr) 1990-02-23 1991-02-22 Composition d'alliage cuivreux
CN91102031A CN1042983C (zh) 1990-02-23 1991-03-28 铜合金系组合物

Publications (3)

Publication Number Publication Date
EP0470262A1 true EP0470262A1 (fr) 1992-02-12
EP0470262A4 EP0470262A4 (en) 1992-08-05
EP0470262B1 EP0470262B1 (fr) 1999-06-16

Family

ID=36778100

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91904341A Expired - Lifetime EP0470262B1 (fr) 1990-02-23 1991-02-22 Composition d'alliage cuivreux

Country Status (11)

Country Link
US (1) US5242511A (fr)
EP (1) EP0470262B1 (fr)
JP (1) JP2702796B2 (fr)
KR (1) KR950007084B1 (fr)
CN (1) CN1042983C (fr)
AT (1) ATE181452T1 (fr)
CA (1) CA2055473C (fr)
DE (1) DE69131337T2 (fr)
HK (1) HK1004870A1 (fr)
RU (1) RU2096847C1 (fr)
WO (1) WO1991013445A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5458702A (en) * 1992-06-30 1995-10-17 Alps Electric Co., Ltd. Alloy powder, dispersion-type conductor using the same
EP1032038A2 (fr) * 1999-02-12 2000-08-30 National Starch and Chemical Investment Holding Corporation Matériau conductrice et résistive électriquement stabil pour utilisation dans des appareils électroniques
FR2811922A1 (fr) * 2000-07-20 2002-01-25 Optoform Sarl Procedes De Prot Composition de pate chargee de poudre metallique, procede d'obtention de produits metalliques a partir de ladite composition, et produit metallique obtenu selon ledit procede
WO2002089152A1 (fr) * 2001-04-25 2002-11-07 National Starch And Chemical Investment Holding Corporation Materiaux conducteurs a stabilite electrique utilises dans des dispositifs electroniques
EP0963558B1 (fr) * 1997-03-01 2003-10-29 Peter Hoffmann Corps en matiere plastique, notamment element plat, pour limiter les reflexions de haute frequence
AT519451B1 (de) * 2017-04-26 2018-07-15 Zkw Group Gmbh Verfahren zur Herstellung zumindest einer elektrisch leitenden Verbindung in einem Schaltungsträger und ein nach diesem Verfahren hergestellter Schaltungsträger
US10388423B2 (en) 2007-09-13 2019-08-20 Henkel Ag & Co. Kgaa Electrically conductive composition
EP4078624A4 (fr) * 2019-12-20 2023-10-18 Henkel AG & Co. KGaA Composition de frittage d'argent contenant un alliage de cuivre pour liaison métallique

Families Citing this family (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4242408C2 (de) * 1991-12-11 1998-02-26 Mitsubishi Electric Corp Verfahren zum Verbinden eines Schaltkreissubstrates mit einem Halbleiterteil
US5372749A (en) * 1992-02-19 1994-12-13 Beijing Technology Of Printing Research Institute Chinese Method for surface treating conductive copper powder with a treating agent and coupler
JP3309231B2 (ja) * 1993-08-25 2002-07-29 タツタ電線株式会社 金属酸化物成形体との密着性の良い導電塗料
US5652042A (en) * 1993-10-29 1997-07-29 Matsushita Electric Industrial Co., Ltd. Conductive paste compound for via hole filling, printed circuit board which uses the conductive paste
JP3536484B2 (ja) * 1995-11-17 2004-06-07 株式会社デンソー 発電機
TW392179B (en) * 1996-02-08 2000-06-01 Asahi Chemical Ind Anisotropic conductive composition
US6488869B2 (en) * 1997-04-08 2002-12-03 Matsushita Electric Industrial Co., Ltd. Conductive paste, its manufacturing method, and printed wiring board using the same
JP3539195B2 (ja) * 1998-03-25 2004-07-07 株式会社村田製作所 導電ペーストおよびそれを用いたセラミック基板の製造方法
US6059894A (en) * 1998-04-08 2000-05-09 Hewlett-Packard Company High temperature flip chip joining flux that obviates the cleaning process
US6086791A (en) * 1998-09-14 2000-07-11 Progressive Coatings, Inc. Electrically conductive exothermic coatings
DE19924683C2 (de) * 1999-05-28 2002-02-28 Betek Bergbau & Hartmetall Verfahren zur Bestückung eines Meißelkopfes eines Schaftmeißels und Meißel
US6337037B1 (en) 1999-12-09 2002-01-08 Methode Electronics Inc. Printed wiring board conductive via hole filler having metal oxide reducing capability
AU2001252557A1 (en) * 2000-04-25 2001-11-07 Hitachi Chemical Co. Ltd. Adhesive for circuit connection, circuit connection method using the same, and circuit connection structure
KR100390638B1 (ko) * 2001-07-09 2003-07-07 남애전자 주식회사 도전성 실리콘 페이스트
TWI325739B (en) * 2003-01-23 2010-06-01 Panasonic Corp Electroconductive paste, its manufacturing method, circuit board using the same electroconductive paste, and its manufacturing method
JP4911975B2 (ja) * 2003-02-17 2012-04-04 ジャパンコンポジット株式会社 導電性樹脂組成物及び燃料電池用セパレーター
US6992001B1 (en) * 2003-05-08 2006-01-31 Kulicke And Soffa Industries, Inc. Screen print under-bump metalization (UBM) to produce low cost flip chip substrate
JP2005171178A (ja) * 2003-12-15 2005-06-30 Tdk Corp 積層セラミック電子部品のスペーサ層用の誘電体ペースト
JP4412013B2 (ja) * 2004-03-16 2010-02-10 Ｔｄｋ株式会社 積層セラミック電子部品用の誘電体ペーストおよび積層セラミック電子部品用の積層体ユニットの製造方法
JP2006080013A (ja) * 2004-09-10 2006-03-23 Mitsui Mining & Smelting Co Ltd 導電性ペースト及びその導電性ペーストを用いて得られるフレキシブルプリント配線板
US20070108419A1 (en) * 2004-11-24 2007-05-17 Tdk Corporation Conductive paste for an electrode layer of a multi-layered ceramic electronic component and a method for manufacturing a multi-layered unit for a multi-layered ceramic electronic component
US20060289839A1 (en) * 2005-06-23 2006-12-28 Emmerson Gordon T Metal salts of organic acids as conductivity promoters
KR100673778B1 (ko) * 2005-08-19 2007-01-24 제일모직주식회사 저온 속경화형 이방성 도전 필름용 조성물, 그로부터제조된 이방성 도전 필름 및 그 제조방법
JP2009068086A (ja) * 2007-09-14 2009-04-02 Tohoku Univ 導電性複合粉末およびその製造方法
CN101246758B (zh) * 2008-03-19 2011-09-14 重庆川仪自动化股份有限公司 用于弱电流的滑动电接触材料
KR100862641B1 (ko) 2008-03-24 2008-10-09 주식회사 나노엠에스이 전자파 차폐 조성물의 제조방법 및 전자파 차폐 조성물
US7857997B2 (en) * 2008-05-28 2010-12-28 Bemis Company, Inc. Conductive ink formulations
JP5217639B2 (ja) * 2008-05-30 2013-06-19 富士通株式会社 コア基板およびプリント配線板
JP5217640B2 (ja) * 2008-05-30 2013-06-19 富士通株式会社 プリント配線板の製造方法およびプリント基板ユニットの製造方法
JP2009290124A (ja) * 2008-05-30 2009-12-10 Fujitsu Ltd プリント配線板
JP2009290135A (ja) * 2008-05-30 2009-12-10 Fujitsu Ltd プリント配線板の製造方法および導電性接合剤
JP5534127B2 (ja) * 2008-05-31 2014-06-25 スリーボンドファインケミカル株式会社 導電性樹脂組成物
JPWO2010004852A1 (ja) * 2008-07-11 2011-12-22 三井金属鉱業株式会社 導電性ペースト用銅粉及び導電性ペースト
US20130059251A1 (en) * 2010-05-18 2013-03-07 Gurunarayan Govind Micro/nano photoconductor
KR101783686B1 (ko) 2010-11-17 2017-10-10 루바타 아플레톤 엘엘씨 알칼리 집전체 애노드
CN103509396B (zh) * 2013-09-15 2016-03-16 浙江大学 疏水抗菌涂层的制备方法
JP5926322B2 (ja) * 2014-05-30 2016-05-25 協立化学産業株式会社 被覆銅粒子及びその製造方法
US10347388B2 (en) * 2015-03-05 2019-07-09 Namics Corporation Conductive copper paste, conductive copper paste cured film, and semiconductor device
CN108602976A (zh) * 2015-08-03 2018-09-28 汉高知识产权控股有限责任公司 通过沉积高导电性组合物实现电磁干扰屏蔽保护
US9637648B2 (en) * 2015-08-13 2017-05-02 E I Du Pont De Nemours And Company Photonic sintering of a solderable polymer thick film copper conductor composition
US9637647B2 (en) * 2015-08-13 2017-05-02 E I Du Pont De Nemours And Company Photonic sintering of a polymer thick film copper conductor composition
CN105655000A (zh) * 2016-01-15 2016-06-08 熊小辉 一种双芯电力导线
CN106449094A (zh) * 2016-09-30 2017-02-22 安徽鑫利源电子有限公司 薄膜电容器接线端子
EP3650499B1 (fr) * 2017-07-07 2023-11-08 Tatsuta Electric Wire & Cable Co., Ltd. Composition de résine électroconductrice et procédé de fabrication d'un emballage blindé l'utilisant
US20190061005A1 (en) * 2017-08-30 2019-02-28 General Electric Company High Quality Spherical Powders for Additive Manufacturing Processes Along With Methods of Their Formation
CN107731434B (zh) * 2017-09-25 2019-07-19 江苏时恒电子科技有限公司 一种热敏电阻铜电极多功能防护膜层及其制备方法
JP7090511B2 (ja) * 2017-09-29 2022-06-24 Ｄｏｗａエレクトロニクス株式会社 銀粉およびその製造方法
US20190355277A1 (en) 2018-05-18 2019-11-21 Aidmics Biotechnology (Hk) Co., Limited Hand-made circuit board
CN110012617A (zh) * 2019-04-03 2019-07-12 东莞塘厦裕华电路板有限公司 一种电路板导通孔制作方法
RU2743934C1 (ru) * 2020-06-15 2021-03-01 Джамиля Викторовна Чайкина Электропроводящая композиция для развивающих игр и способ формирования электропроводящих треков
US11319613B2 (en) 2020-08-18 2022-05-03 Enviro Metals, LLC Metal refinement

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0356867A1 (fr) * 1988-08-23 1990-03-07 Asahi Kasei Kogyo Kabushiki Kaisha Poudres métalliques conductives, procédé pour leur préparation et leur utilisation
JPH03152177A (ja) * 1989-11-09 1991-06-28 Asahi Chem Ind Co Ltd アクリル系導電性ペーストならびに該ペーストを用いた導電体

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3583930A (en) * 1968-04-16 1971-06-08 Chomerics Inc Plastics made conductive with coarse metal fillers
JPS568852A (en) * 1979-07-04 1981-01-29 Nec Corp Semiconductor device
JPS6017392B2 (ja) * 1980-05-01 1985-05-02 福田金属箔粉工業株式会社 銀−銅複合粉末を用いた導電性塗料
JPS58157001A (ja) * 1982-03-15 1983-09-19 東芝ケミカル株式会社 導電性ペ−スト
JPS59146103A (ja) * 1983-02-09 1984-08-21 昭和電工株式会社 ドツテイングペ−スト
JPS6058268A (ja) * 1983-09-08 1985-04-04 Tsudakoma Ind Co Ltd ロ−ラ接触式液剤付与装置のモ−タ制御方法
JPS6280907A (ja) * 1985-04-23 1987-04-14 昭和電工株式会社 導電ペ−スト
JPS61245406A (ja) * 1985-04-24 1986-10-31 昭和電工株式会社 導電ペ−スト
JPS63238230A (ja) * 1987-03-25 1988-10-04 Matsushita Electric Works Ltd 導電性複合材料とその製法
JPS63301405A (ja) * 1987-05-30 1988-12-08 Furukawa Electric Co Ltd:The 低温焼成型導電性ペ−スト及び回路基板の製造方法
JPS6427642A (en) * 1987-07-23 1989-01-30 Kobe Steel Ltd Silver catalyst
JPH01231208A (ja) * 1988-03-11 1989-09-14 Toshiba Chem Corp 導電性ペースト
JPH0241093A (ja) * 1988-07-30 1990-02-09 Nec Home Electron Ltd カラー印刷方法
JPH0241092A (ja) * 1988-07-30 1990-02-09 Sony Corp テレビジヨン装置
US5064469A (en) * 1989-10-03 1991-11-12 Akzo N.V. Preparation of oxidation resistant metal powder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0356867A1 (fr) * 1988-08-23 1990-03-07 Asahi Kasei Kogyo Kabushiki Kaisha Poudres métalliques conductives, procédé pour leur préparation et leur utilisation
JPH03152177A (ja) * 1989-11-09 1991-06-28 Asahi Chem Ind Co Ltd アクリル系導電性ペーストならびに該ペーストを用いた導電体

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of WO9113445A1 *
WORLD PATENTS INDEX LATEST Derwent Publications Ltd., London, GB; AN 91-234152 & JP-A-3 152 177 (ASAHI CHEMICAL) 28 June 1991 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5605560A (en) * 1992-06-30 1997-02-25 Alps Electric Co., Ltd. Method of producing an atomized alloy power
US5458702A (en) * 1992-06-30 1995-10-17 Alps Electric Co., Ltd. Alloy powder, dispersion-type conductor using the same
EP0963558B1 (fr) * 1997-03-01 2003-10-29 Peter Hoffmann Corps en matiere plastique, notamment element plat, pour limiter les reflexions de haute frequence
EP1032038A3 (fr) * 1999-02-12 2002-07-24 National Starch and Chemical Investment Holding Corporation Matériau conductrice et résistive électriquement stabil pour utilisation dans des appareils électroniques
EP1032038A2 (fr) * 1999-02-12 2000-08-30 National Starch and Chemical Investment Holding Corporation Matériau conductrice et résistive électriquement stabil pour utilisation dans des appareils électroniques
WO2002007918A1 (fr) * 2000-07-20 2002-01-31 Optoform Sarl Procedes De Prototypage Rapide Pate chargee de poudre metallique et produits metalliques obtenus avec cette pate
FR2811922A1 (fr) * 2000-07-20 2002-01-25 Optoform Sarl Procedes De Prot Composition de pate chargee de poudre metallique, procede d'obtention de produits metalliques a partir de ladite composition, et produit metallique obtenu selon ledit procede
US6974656B2 (en) * 2000-07-20 2005-12-13 3D Systems, Inc. Paste filled with metal powder and metal products obtained with same
WO2002089152A1 (fr) * 2001-04-25 2002-11-07 National Starch And Chemical Investment Holding Corporation Materiaux conducteurs a stabilite electrique utilises dans des dispositifs electroniques
US6583201B2 (en) 2001-04-25 2003-06-24 National Starch And Chemical Investment Holding Corporation Conductive materials with electrical stability for use in electronics devices
US10388423B2 (en) 2007-09-13 2019-08-20 Henkel Ag & Co. Kgaa Electrically conductive composition
AT519451B1 (de) * 2017-04-26 2018-07-15 Zkw Group Gmbh Verfahren zur Herstellung zumindest einer elektrisch leitenden Verbindung in einem Schaltungsträger und ein nach diesem Verfahren hergestellter Schaltungsträger
AT519451A4 (de) * 2017-04-26 2018-07-15 Zkw Group Gmbh Verfahren zur Herstellung zumindest einer elektrisch leitenden Verbindung in einem Schaltungsträger und ein nach diesem Verfahren hergestellter Schaltungsträger
WO2018195568A1 (fr) * 2017-04-26 2018-11-01 Zkw Group Gmbh Procédé pour établir au moins une liaison électroconductrice dans un support de circuit et support de circuit obtenu selon ledit procédé
EP4078624A4 (fr) * 2019-12-20 2023-10-18 Henkel AG & Co. KGaA Composition de frittage d'argent contenant un alliage de cuivre pour liaison métallique
US12051522B2 (en) 2019-12-20 2024-07-30 Henkel Ag & Co. Kgaa Silver sintering composition containing copper alloy for metal bonding

Also Published As

Publication number Publication date
DE69131337T2 (de) 2000-02-03
WO1991013445A1 (fr) 1991-09-05
DE69131337D1 (de) 1999-07-22
JPH03245404A (ja) 1991-11-01
CN1042983C (zh) 1999-04-14
CA2055473C (fr) 1995-11-14
CN1065280A (zh) 1992-10-14
HK1004870A1 (en) 1998-12-11
ATE181452T1 (de) 1999-07-15
JP2702796B2 (ja) 1998-01-26
EP0470262A4 (en) 1992-08-05
US5242511A (en) 1993-09-07
RU2096847C1 (ru) 1997-11-20
EP0470262B1 (fr) 1999-06-16
KR920701989A (ko) 1992-08-12
KR950007084B1 (ko) 1995-06-30

Similar Documents

Publication Publication Date Title
EP0470262B1 (fr) Composition d'alliage cuivreux
JPH0821254B2 (ja) 銅合金系組成物、それを用いて印刷された成形物、ペーストおよび接着剤
JP4342176B2 (ja) 機能性合金粒子
EP0239901B1 (fr) Composition de pâte conductrice contenant du cuivre
US5204025A (en) Conductive paste composition
JP2643520B2 (ja) 銀含有合金粉末ならびに該粉末を用いた導電性ペースト
JP3578484B2 (ja) 異方導電接続用組成物
JPH0773730A (ja) 導電性粉末
JP3222950B2 (ja) 強固なはんだ付け可能な導電性ペースト
JPH10162647A (ja) 導電性ペースト
JPH07109724B2 (ja) はんだ付け可能な銅系導電性ペースト
JPH1040738A (ja) 導電性ペースト
JP2708606B2 (ja) 銅合金導電性ペースト並びに該ペーストを用いた導電体
EP0425677B1 (fr) Composition pateuse conductrice de l'electricite et son durcissement
JPH0428108A (ja) 銀系導電性ペースト並びに該ペーストを用いた導電体
JPH07331360A (ja) 新規な銅合金粉末及びその製造方法
JPH0428109A (ja) 銅系導電性ペースト並びに該ペーストを用いた導電体
JPH0623582A (ja) リフローはんだ付け可能な導電性ペースト
JPH06223633A (ja) 導電異方性電極接続用組成物および該組成物の硬化膜
JPH0672242B2 (ja) 導電性金属粉体、その製法および用途
JPH03245405A (ja) 銀系合金粉末ならびに該粉末を用いた導電性ペースト
JPS63227671A (ja) 電子線硬化型導電ペ−スト
JP4664046B2 (ja) 導電性回路の形成方法
JPH08216342A (ja) 新規な金属−セラミック複合材
JPH1021742A (ja) 導電性ペースト

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19911023

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE

A4 Supplementary search report drawn up and despatched

Effective date: 19920615

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19951113

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19990616

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990616

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19990616

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990616

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990616

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990616

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990616

REF Corresponds to:

Ref document number: 181452

Country of ref document: AT

Date of ref document: 19990715

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69131337

Country of ref document: DE

Date of ref document: 19990722

ET Fr: translation filed
ITF It: translation for a ep patent filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19991116

Year of fee payment: 10

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000222

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011031

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20020220

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030222

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050222

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20100303

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69131337

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20110222